反应详情

In a oven dried flask (50 mL) was added NaH (60% disepersion in mineral oil) 481 mg (12.03 mmol) under argon. The dispersion was washed 3 times with pentane to remove the mineral oil. To the pure NaH was added 5 mL THF (dry). N-BOC-N-methyl hydroxyl amine (a) 1.53 mg (10.43 mmol) in 5 mL THF was added slowly. The reaction mixture was left for ½ an hour until no more gas production could be seen. The solution was put on ice-bath and stirred for ½ an hour after which 4 g (8.02 mmol) of 4-toluene-sulfonic acid 2-[2-(tert-butyl-diphenyl-silanyloxy)-ethoxy]-ethyl ester (c) was added dropwise. The solution was left on ice-bath for ½ an hour and then stirred over-night at RT. The solvents were removed under reduced pressure, and the residue was dissolved in EtOAc (200 mL) and poured into a separatory funnel. The organic layer was washed with 0.1 M NaOH (5×50 mL), H20 (50 ml), 0.1 m KHSO4, and brine (50 ml) and the dried with MgSO4. After removal of the solvent, the residue was purified using flash chromatography on a Companion Combiflash using a gradient of methanol in DCM (methanol: 0-20% over 19 minutes). Structure confirmed by NMR.

1. customIn a oven dried flask (50 mL)
2. washThe dispersion was washed 3 times with pentane
3. customto remove the mineral oil
4. additionTo the pure NaH was added 5 mL THF (dry)
5. waitThe reaction mixture was left for ½ an hour until no more gas production
6. customThe solution was put on ice-bath
7. additionwas added dropwise
8. waitThe solution was left on ice-bath for ½ an hour
9. customThe solvents were removed under reduced pressure
10. dissolutionthe residue was dissolved in EtOAc (200 mL)
11. additionpoured into a separatory funnel
12. washThe organic layer was washed with 0.1 M NaOH (5×50 mL), H20 (50 ml), 0.1 m KHSO4, and brine (50 ml)
13. dry with materialthe dried with MgSO4
14. customAfter removal of the solvent
15. customthe residue was purified
16. customa gradient of methanol in DCM (methanol: 0-20% over 19 minutes)